Model calculation and empirical investigation of enhanced field emission behavior of branched carbon nanostructures

In this paper, we propose the novel branched carbon nanotubes (B-CNTs) as efficient candidate for field emission applications. We believe that the double-stage structure of B-CNTs, beside formation of multiple thin branches at the apex of each vertical CNT, is responsible for the observed enhanced field emission behavior in B-CNTs. In this regard, we have derived an analytical model to evaluate the field enhancement factor (β) of the B-CNTs in comparison with CNTs, as the most popular cathode for field emission applications in the scientific society. The presented model also allows investigating the effect of different structural parameters on the field emission characteristic. We have also, compared the field emission characteristics of the B-CNTs with vertical CNTs experimentally. We observed a β value for B-CNTs which was around three times higher than CNTs. The observed enhancement in the experimental data was in good agreement with the presented analytical model.     

Effect of deposition voltage on the field emission properties of electrodeposited diamond-like carbon films

Diamond-like carbon (DLC) films were deposited on Al substrates by electrodeposition technique under various voltages. The surface morphology and compositions of synthesized films were characterized by scanning electron microscopy and Raman spectroscopy. With the increase of deposition voltage, the sp² phase concentration decreased and the surface morphology changed dramatically. The influence of deposition voltage on the field electron emission (FEE) properties of DLC films was not monotonic due to two adverse effects of deposition voltage on the surface morphology and compositions. The DLC film deposited under 1200 V exhibited optimum FEE property, including a lowest threshold field of 13 V/μm and a largest emission current density of 904.8 μA/cm² at 23.5 V/μm.     

AuPd纳米粒子作为催化剂制备硼纳米线及其场发射性质

利用化学气相沉积法,采用不同组分的金属合金纳米粒子AuPd作为催化剂,在Si(111)基底上成功制备大面积、高密度的硼纳米线薄膜.纳米线的平均长度约为10μm,直径在50—130 nm之间.结构分析表明,纳米线为单晶结构,硼纳米线的直径随着元素Pd在合金催化剂中比例的增加而减少.场发射特性测试结果表明,通过调整催化剂组分可以实现对硼纳米线的尺寸和密度的调控.     

Enhanced field emission properties of screen-printed doubled-walled carbon nanotubes by polydimethylsiloxane elastomer

Field emission (FE) properties of double-walled carbon nanotubes (DWCNTs) treated by polydimethylsiloxane (PDMS) elastomer with different heating temperature have been systematically studied. The current density of treated DWCNT films decreases with the increase of heating temperature. The screen-printed DWCNTs treated by PDMS elastomer with drying temperature 150 °C for 20 min have the best FE performance with a marvelous field enhancement factor (β = 20194). The optimized FE performance is attributed to the morphological change of DWCNT films after PDMS elastomer treatment and the change of separation energy for the CNT-substrate interface. It is proved that the PDMS treatment is a facile and effective method for field emission display (FED) application, especially for low-temperature FED preparation.     

Influence of field evaporation treatment on the field emission properties of carbon nanotubes array

Field evaporation was used in the post-fabrication treatment of a carbon nanotubes (CNTs) array and effectively modified the CNTs morphology in favor of the field emission under a moderate field. After the field evaporation treatment, the uniformity of the emission site distribution improved but the onset voltage rose. Using the Fowler-Nordheim theory, the actual onset field and the evaporation field around the CNT were calculated to be −4.6-5 and 9-12 V/nm, respectively. These values are close to those obtained from the individual CNT samples. The above results have provided an alternative to modify the configuration of an array sample and demonstrated the feasibility of tackling the problem of the disparity in the field emission capability of different CNTs in an array.     

碳纳米管阴极强流脉冲发射放气特性研究

为了研究碳纳米管(CNT)阴极强流脉冲发射特性, 在2MeV直线感应加速器(LIA)注入器平台上开展了阴极放气特性实验. 研究结果表明：碳纳米管阴极强流发射时伴随有严重的阴极放气, 阴极放气参与形成阴极等离子体. 对于特定的几次实验, 通过数值积分估算了阴极材料的放气量为0.8—1.12Pa·L, 释放的气体分子数目与电子数目之比为254—203, 说明阴极等离子体为弱电离等离子体. 分析了二极管电压、发射电流密度、放气量以及放气分子数目/电子数目之间的关系     

界面势垒对碳纳米管场发射特性的影响

以界面势垒对碳纳米管(CNT)场发射的影响为研究目的,在硅衬底上引进很薄的二氧化硅层,以二氧化硅层作为绝缘势垒,然后在二氧化硅界面层上直接生长CNT,来研究二氧化硅绝缘势垒层对CNT场发射的影响。场发射结果为:Fowler-Nordheim(F-N)曲线分为两部分,高电场下偏离F-N曲线并趋于饱和。在双势垒模型的基础上,从电场在两势垒上的分布不同及电子在两势垒上的隧穿几率不同,理论上分析了界面势垒对场发射的影响:低电场下电子在界面势垒的隧穿几率大于在表面势垒的隧穿几率,界面势垒对场发射不起阻碍作用,场发射遵守F-N规律;高电场下电子在界面势垒的隧穿几率小于在表面势垒的隧穿几率,场发射偏离F-N规律。理论对实验结果进行了合理的解释。     

Improve the field emission uniformity of carbon nanotubes treated by ball-milling process

Carbon nanotubes (CNTs) deposited by chemical vapor deposition (CVD) were treated by ball milling. The morphologies and field emission properties of the treated CNTs depending on milling time were studied. The emission turn-on field is increased, and the field emission current density is reduced, when the milling time increased from 0.5 to 3 h. The as-deposited long CNTs were cut to short CNTs (∼1 h) and micro-particles (>1 h) with increasing of the milling time. It is found that the optimized milling time is 0.5-1 h, the treated CNTs showed excellent field emission properties, such as low turn-on field, high emission current density and uniform luminescence spots distribution.     

界面势垒对碳纳米管场发射特性的影响

以界面势垒对碳纳米管(CNT)场发射的影响为研究目的,在硅衬底上引进很薄的二氧化硅层,以二氧化硅层作为绝缘势垒,然后在二氧化硅界面层上直接生长CNT,来研究二氧化硅绝缘势垒层对CNT场发射的影响。场发射结果为：Fowler-Nordheim(F-N)曲线分为两部分,高电场下偏离F-N曲线并趋于饱和。在双势垒模型的基础上,从电场在两势垒上的分布不同及电子在两势垒上的隧穿几率不同,理论上分析了界面势垒对场发射的影响：低电场下电子在界面势垒的隧穿几率大于在表面势垒的隧穿几率,界面势垒对场发射不起阻碍作用,场发射遵守F-N规律;高电场下电子在界面势垒的隧穿几率小于在表面势垒的隧穿几率,场发射偏离F-N规律。理论对实验结果进行了合理的解释。     

Effects on the field emission properties by variation in surface morphology of patterned photosensitive carbon nanotube paste using organic solvent

Photosensitive carbon nanotube (CNT) paste was prepared by 3-roll milling of multi-walled carbon nanotubes (MWNTs), UV-sensitive binder solution, and Ag as filler additives. Arrays of MWNT dots with a diode structure were fabricated by a combination of screen printing method and photolithography using these paste, and acetone utilized as the developer. The MWNT dots were well-defined and the organic binder materials in the dots were partially removed. The MWNT film without a heat treatment showed a high current density of 1.35 mA/cm² at 3.25 V/μm and low turn-on field of 2.2 V/μm at 100 μA/cm². Acetone can be used as an efficient developer to form patterns and to remove the organic residues in patterns, simultaneously.     

Simulation and fabrication of carbon nanotubes field emission pressure sensors

A novel field emission pressure sensor has been achieved utilizing carbon nanotubes (CNTs) as the electron source. The sensor consists of the anode sensing film fabricated by wet etching process and multi-wall carbon nanotubes (MWNTs) cathode in the micro-vacuum chamber. MWNTs on the silicon substrate were grown by thermal CVD. The prototype pressure sensor has a measured sensitivity of about 0.17-0.77 nA/Pa (101-550 KPa). The work shows the potential use of CNTs-based field-emitter in microsensors, such as accelerometers and tactile sensors.     

Growth and field emission properties of globe-like diamond microcrystalline-aggregate

The globe-like diamond microcrystalline-aggregates were fabricated by microwave plasma chemical vapor deposition (MPCVD) method. The ceramic with a Ti mental layer was used as substrate. The fabricated diamond was evaluated by Raman scattering spectroscopy, X-ray diffraction spectrum (XRD), and scanning electron microscope (SEM). The field emission properties were tested by using a diode structure in a vacuum. A phosphor-coated indium tin oxide (ITO) anode was used for observing and characterizing the field emission. It was found that the globe-like diamond microcrystalline-aggregates exhibited good electron emission properties. The turn-on field was only 0.55 V/μm, and emission current density as high as 11 mA/cm² was obtained under an applied field of 2.9 V/μm for the first operation. The growth mechanism and field emission properties of the globe-like diamond microcrystalline-aggregates are discussed relating to microstructure and electrical conductivity.     

Modeling and simulation for the field emission of carbon nanotubes array

To optimize the field emission of the infinite carbon nanotubes (CNTs) array on a planar cathode surface, the numerical simulation for the behavior of field emission with finite difference method was proposed. By solving the Laplace equation with computer, the influence of the intertube distance, the anode–cathode distance and the opened/capped CNT on the field emission of CNTs array were taken into account, and the results could accord well with the experiments. The simulated results proved that the field enhancement factor of individual CNT is largest, but the emission current density is little. Due to the enhanced screening of the electric field, the enhancement factor of CNTs array decreases with decreasing the intertube distance. From the simulation the field emission can be optimized when the intertube distance is close to the tube height. The anode–cathode distance hardly influences the field enhancement factor of CNTs array, but can low the threshold voltage by decreasing the anode–cathode distance. Finally, the distribution of potential of the capped CNTs array and the opened CNTs array was simulated, which the results showed that the distribution of potential can be influenced to some extent by the anode–cathode distance, especially at the apex of the capped CNTs array and the brim of the opened CNTs array. The opened CNTs array has larger field enhancement factor and can emit more current than the capped one.     

碳纤维阴极的场致发射特性实验研究

 研究了具有一定导电性能的碳纤维的直流场致发射电子束特性,实验分别在大气环境、低真空（10^-1 Pa）及高真空(10^-5 Pa)环境下进行。实验结果表明,碳纤维具有一定的场致发射能力,并且发射特性和发射环境的真空度密切相关。在大气环境下,发射电子束流与所施加的电压符合Fowler-Nordheim关系,当电压为7 kV,电流为61.4 μA时,根据Fowler-Nordheim定理推算出碳纤维场致发射场增强因子为3.75×10⁵。在低真空条件下阳极只收集到微弱的电流;在高真空条件下,阴极发射明显,在较低电压下就能观测到阳极电流,放电前阳极最高电流是大气条件下的3~4倍,发射的束流大小和所施加在尖端的电压关系接近Child-Langmiur定律。     

Field electron emission images of multi-walled carbon nanotubes

Field electron emission microscope images from multi-walled carbon nanotubes can typically be characterized by the presence of five pentagons surrounding a sixth central pentagon. The observations of bright line centered interference patterns between adjacent pentagons in the field electron emission microscope images of multi-walled carbon nanotubes have been reported in the literature. We have observed a shift from bright to dark line centered interference patterns and associated this with the presence of surface adsorption. In order to identify the origin of the contaminant, multi-walled carbon nanotubes were dosed with H₂, H₂O, CO and O₂ and then imaged in the field electron emission microscope. Only the samples exposed to O₂ showed a shift from a bright line centered pattern between adjacent pentagons of a clean surface to a dark line centered pattern when one pentagon was contaminated or a bright line centered pattern when both adjacent pentagons become contaminated. The results of the experimental studies and the modeling of the changes in the field emission pattern as phase shifts in the wave function of the tunneling electrons due to modifications in the surface work function are presented.     

碳纳米管场致电子发射新机制

基于对长达 1μm的 (5 ,5 )碳纳米管的量子力学计算 ,作者发现使碳纳米管具有优异场致电子发射特性的因素除了人们预期的尖端场增强之外 ,电荷在纳米管尖端的积累造成有效功函数 (真空势垒 )的非线性下降也起了非常重要的作用 .对外加电场Vappl=10— 14V/ μm下的碳纳米管进行了计算 ,得到与实验结果相近的发射电流     

Field emission characteristics of carbon nanotubes post-treated with high-density Ar plasma

The field emission characteristics of carbon nanotubes (CNTs) grown by thermal chemical vapor deposition (CVD) and subsequently surface treated by high-density Ar plasma in an inductively coupled plasma reactive ion etching (ICP-RIE) with the various plasma powers were measured. Results indicate that, after treated by Ar plasma with power between 250 and 500 W, the emission current density of the CNTs is enhanced by nearly two orders of magnitude (increased from 0.65 to 48 mA/cm²) as compared to that of the as-grown ones. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to investigate the structural features relevant to the modified field emission properties of CNTs. The SEM images of CNTs subjected to a 500 W Ar plasma treatment exhibit obvious damages to the CNTs. Nevertheless, the turn-on fields decreased from 3.6 to 2.2 V/μm, indicating a remarkable field emission enhancement. Our results further suggest that the primary effect of Ar plasma treatment might be to modify the geometrical structures of the local emission region in CNTs. In any case, the Ar plasma treatment appears to be an efficient method to enhance the site density for electron emission and, hence markedly improving the electric characteristics of the CNTs.     

N-doped graphene as a nanostructure adsorbent for carbon monoxide: DFT calculations

ABSTRACT

This work reports the physisorption of carbon monoxide (CO) on the surface of N-doped graphene. To study the adsorption of CO on N-doped graphene, some quantum chemical calculations were used through density functional theory. Based on our results, it can be found that the CO molecule could be adsorbed on the surface of N-doped graphene physically with the adsorption energies (E_ads) of ?2.9 and ?0.8 kcal mol^?1 (depends on the kind of configuration) while positive adsorption energies were calculated upon adsorption of CO on pristine graphene. We used the charge analysis for calculation of the net transferred charge of adsorbed CO on pristine and N-doped graphene sheets to evaluate the sensing ability of surface. The global indices of reactivity were calculated from the differences of the lowest unoccupied molecular orbital and highest occupied molecular orbital energies. Graphs for density of states point to some orbital hybridisation between CO molecule and N-doped graphene. Consequently, the N-doped graphene transforms the existence of CO molecules into electrical signal, and it may be potentially used as a sensor for CO.     

Mechanism of field electron emission from carbon nanotubes

Field electron emission (FE) is a quantum tunneling process in which electrons are injected from materials (usually metals) into a vacuum under the influence of an applied electric field. In order to obtain usable electron current, the conventional way is to increase the local field at the surface of an emitter. For a plane metal emitter with a typical work function of 5 eV, an applied field of over 1 000 V/μm is needed to obtain a significant current. The high working field (and/or the voltage between the electrodes) has been the bottleneck for many applications of the FE technique. Since the 1960s, enormous effort has been devoted to reduce the working macroscopic field (voltage). A widely adopted idea is to sharpen the emitters to get a large surface field enhancement. The materials of emitters should have good electronic conductivity, high melting points, good chemical inertness, and high mechanical stiffness. Carbon nanotubes (CNTs) are built with such needed properties. As a quasi-one-dimensional material, the CNT is expected to have a large surface field enhancement factor. The experiments have proved the excellent FE performance of CNTs. The turn-on field (the macroscopic field for obtaining a density of 10 μA/cm²) of CNT based emitters can be as low as 1 V/μm. However, this turn-on field is too good to be explained by conventional theory. There are other observations, such as the non-linear Fowler-Nordheim plot and multi-peaks field emission energy distribution spectra, indicating that the field enhancement is not the only story in the FE of CNTs. Since the discovery of CNTs, people have employed more serious quantum mechanical methods, including the electronic band theory, tight-binding theory, scattering theory and density function theory, to investigate FE of CNTs. A few theoretical models have been developed at the same time. The multi-walled carbon nanotubes (MWCNTs) should be assembled with a sharp metal needle of nano-scale radius, for which the FE mechanism is more or less clear. Although MWCNTs are more common in present FE applications, the single-walled carbon nanotubes (SWCNTs) are more interesting in the theoretical point of view since the SWCNTs have unique atomic structures and electronic properties. It would be very interesting if people can predict the behavior of the well-defined SWCNTs quantitatively (for MWCNTs, this is currently impossible). The FE as a tunneling process is sensitive to the apex-vacuum potential barrier of CNTs. On the other hand, the barrier could be significantly altered by the redistribution of excessive charges in the micrometer long SWCNTs, which have only one layer of carbon atoms. Therefore, the conventional theories based upon the hypothesis of fixed potential (work function) would not be valid in this quasi-one-dimensional system. In this review, we shall focus on the mechanism that would be responsible for the superior field emission characteristics of CNTs. We shall introduce a multi-scale simulation algorithm that deals with the entire carbon nanotube as well as the substrate as a whole. The simulation for (5, 5) capped SWCNTs with lengths in the order of micrometers is given as an example. The results show that the field dependence of the apex-vacuum electron potential barrier of a long carbon nanotube is a more pronounced effect, besides the local field enhancement phenomenon.     

Growth of carbon nanotubes using nanocrystalline carbon catalyst

The basic growth of carbon nanotubes (CNTs) involves dissociation of hydrocarbon molecules over a metal layer as a catalyst. Generally, the metals used for the catalyst include nickel, cobalt, gold, iron, platinum, and palladium. However, the metal catalyst used with CNTs could have a harmful influence on the electrical properties of electronic devices. Therefore, we propose the use of nanocrystalline carbon (nc-C) as the catalyst for the growth of CNTs. We used a nc-C catalyst layer deposited by the closed-field unbalanced magnetron (CFUBM) sputtering method, and CNTs were grown by the hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment and acetylene gas (C₂H₂) as a carbon source. The CNTs were grown on the nc-C layers pretreated with a variation of the pretreatment time. The characteristics of the pretreated nc-C layers and the grown CNTs were investigated by field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM) measurements. Also, the structural variation of the pretreated nc-C layers was investigated by Raman measurement. We used the nc-C catalyst without metal, and we confirmed that our CNTs were composed with only carbon elements through an EDS measurement. Also, the pretreatment time was attributed to the growth of CNTs.